Physical Mechanism of Sono-Fenton Process

Sankar Chakma and Vijayanand S. Moholkar

Dept. of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781 039, Assam, India

DOI 10.1002/aic.14150
Published online in Wiley Online Library (wileyonlinelibrary.com)

Hybrid advanced oxidation processes (AOPs), where two or more AOPs are applied simultaneously, are known to give
effective degradation of recalcitrant organic pollutants. This article attempts to discern the physical mechanism of the
hybrid sono-Fenton process with identification of links between individual mechanism of the sonolysis and Fenton pro-
cess. An approach of coupling experimental results with simulations of cavitation bubble dynamics has been adopted for
two textile dyes as model pollutants. Fenton process is revealed to have greater contribution than sonolysis in the over-
all decolorization of both dyes. H2O2 added to the liquid medium as a Fenton reagent scavenges • OH radicals produced
by cavitation bubbles. Addition of only H2O2 to the medium during sonolysis does not yield marked difference in decol-
orization. Elimination of transient cavitation with application of elevated static pressure to the medium does not alter
the extent of decolorization. The synergy between sonolysis and Fenton process is, thus, revealed to be negative. The
dissolved oxygen in the medium is found to play an important role in decolorization through conservation of oxidizing
C 2013 American Institute of Chemical Engineers AIChE J, 00: 000–000, 2013
radicals. V
Keywords: fenton process, advanced oxidation process, cavitation, sonolysis, decolorization

Introduction The combinations of AOPs that have been used includes

Use of synthetic organic dyes by the textile industries has
increased significantly in recent years and many of these
dyes are toxic organic pollutants. Based on their chemical
structure, the synthetic dyes are categorized into various
classes like acidic, basic, azo, nonazo etc. Among these
classes, use of azo dyes has been the maximum (70%).1
These dyes appear in the wastewater discharge from textile
industries. The degradation (or decolorization) of these dyes
using conventional biological techniques is very difficult due
to their complex structure. Globally, approximately 10,000
types of dyes and pigments are produced annually, and about
20% of these are discharged as textile industrial effluents
without any pretreatment. For the effective decolorization of
the synthetic dyes, advanced oxidation processes (AOPs)
have been widely employed as alternative methods. These
techniques include Fenton, ozonation, photocatalytic techni-
ques, peroxide treatment, sonolysis, enzyme treatments, etc.
Literature published in the last decade includes more than
100 papers that report the use of these techniques for decol-
orization of textile wastewater, containing a wide range of
dyes belonging to the different classes mentioned previously.
For further boosting, the efficiency of AOPs, hybrid methods
have also been widely used that simultaneously employ two
or more AOPs mentioned previously and voluminous litera-
ture has also been published in this area in the past decade.
Additional Supporting Information may be found in the online version of this
article.
Correspondence concerning this article should be addressed to V. S. Moholkar
at vmoholkar@iitg.ac.in.
C 2013 American Institute of Chemical Engineers
V of an advanced oxidation process such as sonolysis or
sono-Fenton, sono-photocatalysis, sono-enzymatic treatments,
photo-Fenton techniques, UV/H2O2, UV/ozone, ozone/H2O2,
etc.2–5 An excellent review of the individual as well as
hybrid AOP techniques for treatment of wastewater has been
given by Gogate and Pandit.6,7 The hybrid techniques have
been reported to enhance the decolorization kinetics as well
as yield. Most of the literature in the area of hybrid AOPs is
focused on results than rationale. Although in many articles
an attempt is made to quantify the enhancement factor for
the decolorization (or degradation) with reference to one of
the AOPs, only a few studies have attempted to deduce the
exact mechanism of the synergism between the individual
AOP. In this article, we have addressed this basic issue in
the context of a widely used hybrid AOP, i.e., sono-Fenton
process. Several recent articles report employment of sono-
Fenton processes for degradation of different organic pollu-
tants.8–19 We have used two dyes, viz. Acid red B (an azo
dye, abbreviated hereafter as ARB) and Blue HE2R (a non-
azo dye, abbreviated hereafter as BLH), as model pollutants
in this study in view of the large pollution generated by
effluent from textile industry, as mentioned earlier. Our
approach for identifying the mechanism of the synergism
between sonolysis and Fenton process is twofold, i.e., to
couple experiments with simulations of cavitation bubble
dynamics. In the next section, we present our contemplations
and conjectures, on which the methodology and protocols of
this study are based.
Contemplations and Conjectures
The degradation (or oxidation or decolorization) efficiency

AIChE Journal 2013 Vol. 00 No. 00 1

Fenton reagent is characterized by the production of • OH
radical, which is a powerful oxidizing agent with an oxida-
tion potential of 2.33 V. The • OH radicals are extremely
reactive species, and the typical rate constant of their reac-
tion with organic compounds ranges between 1062109
mol21 s21.20 However, the basic mechanism (either physical
or chemical) through which • OH radicals are produced in
these techniques is completely different. In sonolysis, the
radicals are produced through transient cavitation, which is a
phenomenon comprising essentially of three phases, viz.
nucleation, growth and an adiabatic implosive collapse of a
gas or vapor bubble.21 These phases are driven by pressure
variation induced in the liquid medium (or solvent) due to
propagation of the ultrasound wave. Gas pockets trapped in
the crevices of solid boundaries of the reaction system con-
stitute the nuclei for cavitation. The growth of the bubble is
accompanied by evaporation of large amount of solvent at
the bubble interface (or bubble wall), and diffusion of sol-
vent vapor toward the core of the bubble. During the ensuing
collapse phase, not all of the vapor molecules can diffuse
back to the bubble wall and condense.22 A significant frac-
tion of vapor remains inside the bubble when the bubble
motion reaches extremely fast during the final moments of
compression. The bubble collapse occurs within as small
time as 50 ns, and it is almost adiabatic. The temperature
and pressure condition inside the bubble reaches extreme,
typically excessive of 5000 K and 500 bar, respectively.23,24
The entrapped solvent vapor inside the bubble is subjected
to these extreme conditions and undergoes thermal dissocia-
tion resulting in very many chemical species, some of which
are radical species. The solvent used in majority of
the sonochemical processes is water, and 8 species could
result out of thermal dissociation of water, viz.
H2 ; O2 ; H2 O2 ; O3 ; • OH; H• ; O• ; HO•2 . The predominant radi-
cal species is • OH.22–24 As the bubble reaches minimum
radius during the radial motion, these species can either dif-
fuse out of the bubble, or with fragmentation of the bubble
these get released and mixed into the medium.
•
OH radical production through Fenton process is known
to occur through the well-known reactions as follows20
Fe21 1 H2 O2 ! Fe31 1 OH2 1 HO•
Fe31 1 H2 O2 ! Fe21 1 HO•2 1 H1
Fe31 1 HO•2 ! Fe21 1 O2 1 H1
When the techniques of sonolysis and Fenton are applied
together, there are several means through which they can
assist/oppose each other’s mechanism. One obvious mecha-
nism through which the two AOPs can interact is the forma-
tion and utilization of • OH radicals. These radicals are
formed at the location of bubble collapse and can independ-
ently decolorize the dye molecules. However, being
extremely reactive, these radicals do not penetrate or diffuse
through the bulk medium. If the concentration of pollutant in
the solution is small, the probability of interaction between
the radical and pollutant molecule is also small, and under
these circumstances
 • it is very likely
 that the • OH radicals
would recombine 2 OH $ H2 O2 to give H2O2, which is a
loss of oxidation potential. However, with Fe21 being pres-
ent in the medium, • OH radicals can get regenerated from
the H2O2 (formed due to recombination) through Fenton
reactions. Any mechanical agitation applied to the medium
2 DOI 10.1002/aic Published on behalf of the AIChE
can enhance the probability of radical-pollutant interaction,
which in turn results in enhancement of degradation/decolor-
ization. Ultrasound and cavitation also generate intense
micromixing in the medium through different mechanisms
such as microturbulence due to cavitation bubbles and
microstreaming (i.e., oscillatory velocity of fluid elements
due to ultrasound propagation).21 This micromixing can
increase the probability of interaction of radical and pollutant
molecules, resulting in better utilization of the radicals (gen-
erated from either Fenton process or from the cavitation bub-
bles) for purpose of decolorization. If, however, H2O2 added
externally to the medium (as one of the Fenton reagents) is
in excess, it would evaporate into the cavitation bubble gen-
erating additional • OH radicals, which could enhance the
extent of decolorization. The extent of production of radicals
through cavitation bubbles depends on three factors25 (1) the
bubble population in the medium, (2) extent of evaporation
of H2O2, which in turn depends on the concentration of
H2O2 in the solution and its partial pressure, and (3) peak
temperature and pressure reached in the bubble at transient
collapse, which in turn depends on frequency and pressure
amplitude of the ultrasound wave. It should be noted that
excess concentration of H2O2 in the medium could have
adverse effect on degradation/decolorization as the • OH radi-
cals generated by either cavitation bubbles or Fenton reac-
tions can get converted to molecular species due to
scavenging action of H2O2 through following reactions26
•
OH 1 H2 O2 ! H2 O 1 HO•2
•
OH 1 HO•2 ! O2 1 H2 O
The dissolved oxygen in the medium also plays a critical
role in the decolorization process due to the conservation of
radicals, as has been demonstrated in our earlier works.27,28
The dissolved oxygen can help conservation of the • OH radi-
cals generated through Fenton reactions as well as cavitation
bubbles through following reaction
•
OH 1 O2 $ O• 1 HO•2
The physical mechanism of synergy between sonolysis
and Fenton reactions can be deduced by discriminating
between the physical and chemical effects of ultrasound and
cavitation, each of which has distinct beneficial influence on
the Fenton process. The question that we try to answer is
that what is the individual contribution of these effects, and
which of these effects is more beneficial for the hybrid pro-
cess of sono-Fenton. Moreover, we also try to identify the
role played by secondary factors such as concentration of
H2O2 in the medium and extent of dissolved oxygen content
in the medium. As stated previously, we have adopted an
approach of coupling experimental results with simulations
of bubble dynamics for this purpose.
Materials, Methods and Simulations
This study aimed at elucidating the physical mechanism of
the sono-Fenton process, i.e., identifying the interconnections
between cavitation physics and Fenton chemistry. The textile
dyes used in this work are only model or representative pol-
lutants. The degradation of these dyes with sono-Fenton pro-
cess has been previously reported in literature with
identification of the degradation intermediates.2 In view of
2013 Vol. 00 No. 00 AIChE Journal
this, we have not included identification of degradation inter-
mediates (with proposition of the degradation mechanism) in
the experimental scope of this study. Experiments have been
designed so as to vary the characteristics of cavitation phe-
nomenon in the medium. The decolorization of original dye
solution has been used as yardstick for illuminating the phys-
ical mechanism and synergy of the sono-Fenton process.
Materials
Following chemicals have been used in this study: ARB
dye, BLH dye, ferrous sulfate heptahydrate (FeSO47H2O),
hydrogen peroxide (30% v/v), sulfuric acid (97%), sodium
hydroxide (pellets). All the chemicals were purchased from
Merck and used as received without any further pretreatment.
For all experiments, Milli-Q water from Milli-Q Synthesis
R
unit (MilliporeV, USA) was used as the liquid medium.
Experimental setup
A schematic of the experimental setup is given online in
the supplementary material. Sonication experiments were
carried out in a conical flask (250 mL) made of borosilicate
glass. Experiments were carried out with either mechanical
stirring of the solution or sonication. For mechanical stirring,
a magnetic stirrer (Remi Equipments, Model: LZMS3969)
was used. An ultrasound bath (Jeotech, Model: UC-10,
Capacity: 10 L) with frequency of 40 kHz and power of
200 W was used for sonication the medium. The bath was
filled with 10 L of water as the sonication medium. This
water was replaced with fresh water in every 10 min to
maintain bulk liquid medium at constant temperature during
the experiment. The average temperature of the bath, and,
hence, the reaction solution inside the flask, varied by less
than 3 C due to this procedure. Prior to the experiments, the
sonication bath was characterized with calorimetric measure-
ments for actual power dissipation and the distribution of
acoustic pressure amplitude.25,29 The ultrasound intensity
(and, hence, the ultrasound pressure amplitude) in the bath
shows significant spatial variation. To avoid the variation in
the ultrasound pressure amplitude in different experiments
(which could give rise to artifacts), the conical flask contain-
ing dye solution was placed at the center of the sonication
bath, and its position was carefully maintained constant in
all experiments. All sonication experiments were conducted
in the same flask so as to have same ultrasound pressure
amplitude and power dissipation in the reaction mixture in
all experiments. Moreover, sonication experiments were car-
ried out at two static pressures, viz. atmospheric (101.3 kPa)
static pressure and elevated static pressure of 200 kPa (or 2
bar). The rationale underlying raised static pressure to the
system during sonication has been described in an earlier
article,30 and will also be explained in this article subse-
quently. A simple procedure was used to raise the static
pressure of the medium. The neck of the conical flask used
in the experiments was closed using a rubber stopper with
metal tube pierced in it. The outer end of the metal tube was
connected to a nitrogen cylinder through two-stage pressure
regulator. The pressure of the outlet gas from cylinder, and,
hence, the static pressure on the dye solution could be con-
trolled through this regulator.
Experimental procedure
A 100 ppm stock solution of the dye (both ARB and
BLH) was prepared and stored at 4 C. The major
AIChE Journal 2013 Vol. 00 No. 00 Published on behalf of the AIChE
experimental parameters that influence the decolorization
process are (1) composition of the Fenton reagent (i.e., the
ratio of Fe21/H2O2), (2) the initial concentration of dye, and
(3) pH of the solution. To assess the optimum values of
these parameters, we conducted preliminary experiments
with ARB dye, which have been described online in the sup-
plementary material.
For all experiments, 50 mL of dye solution of concentra-
tion 10 ppm was prepared by taking an appropriate amount
of stock solution and diluting it with Milli-Q water. The
experiments were carried out in seven categories for both
dyes with different conditions, as described in Table 2. Prior
to the main set of experiments, we conducted several prelim-
inary experiments in which the influence of parameters such
as initial dye concentration, ratio of Fenton reagents (i.e.,
H2O2 and FeSO4  7H2O) and pH of the solution was
assessed. The optimum value of each parameter was decided
on the basis of these preliminary experiments (see supple-
mentary material for greater details) and was further used for
the main set of experiments. To monitor the progress of
decolorization of dye solution, aliquots of 1 mL were with-
drawn from the reaction mixture every 10 min, and the total
time of treatment of dye solution in each category of experi-
ments was 60 min. During the withdrawal of the aliquot, the
pressure in the conical flask was released. The pressure was
restored prior to commencement of sonication. After with-
drawal of aliquot, the Fenton reaction was terminated by
adjusting the pH 7.5– 8.0 with NaOH stock solution (5 N),
which also resulted in Fe(III) floc formation. The samples
were then filtered through 0.22 lm filter to remove the
Fe(III) floc and the filtrate was analyzed for the concentra-
tion of dye using UV–visible spectrophotometer (Varian
Carry 50). The maximum absorbance wavelength (kmax) of
ARB and BLH were determined at 512 nm and 586 nm,
respectively, by scanning the UV–vis spectra from 200 to
800 nm. Figures 1A and B depict the UV-vis spectra of sam-
ples of the dye solutions withdrawn from the reaction mix-
tures at different time intervals. The decolorization efficiency
in different experimental categories was determined as
g ð%Þ5ðCo 2CÞ=Co 3100, where, Co is the initial concentra-
tion of dye, and C is the concentration of dye at any time t
(min). In each of the seven categories of experiments for
both dyes, experimental runs were taken in triplicate to
check the reproducibility of the results. The mean value of
the three experimental runs was used for evaluation of
kinetics of decolorization and the final yield.
Bubble Dynamics Model
Cavitation is essentially the nucleation, growth and implo-
sive collapse of gas bubbles (or more generally, the radial
motion or volume oscillations of the bubble) driven by bulk
pressure variation induced by ultrasound. Depending on the
pressure amplitude of the ultrasound wave and static pressure
in the medium, the radial motion of the bubble is character-
ized as stable cavitation and transient cavitation. The tran-
sient collapse of the bubble is extremely fast and adiabatic
during which the bubble wall velocity reaches (or even
exceeds) the sonic speed in the liquid medium. The bubble
can get compressed to an extremely small size (typically 1/
10th to 1/100th of original size), and temperature and pres-
sure in it can reach to extreme (5000 K, 500 bar). This
essentially creates energy concentration in the medium on
extremely small spatial and temporal scale, as the bubble
DOI 10.1002/aic 3

Figure 1. (A) UV–visible spectra of ARB for different
samples withdrawn at different time interval
during Fenton reaction, and (B) UV–visible
spectra of BLH for different samples
withdrawn at different time interval during
Fenton reaction.
collapse occurs in a few tens of nanoseconds. During the
transient collapse, the bubble contents (which is a mixture of
gas and vapor of bulk liquid medium) are subjected to
extreme conditions generated in the bubble and can get dis-
sociated to form various species, some of which are radical
species. The most common liquid medium used for cavita-
tion assisted reactions is water and the species arising out of
dissociation of water contain many radicals such as H• , O•
and • OH. For small bubbles of few microns size and fre-
quencies in the range of 20–100 kHz, transient cavitation is
seen for ultrasound pressure amplitudes greater than the
static pressure on the medium. If the static pressure of the
medium is raised to moderate levels, keeping the acoustic
pressure amplitude constant, the transient cavitation events
get eliminated as the static pressure exceeds the ultrasound
pressure amplitude. In such cases, the bubble undergoes sta-
ble, small-amplitude oscillatory motion. The temperature and
4 DOI 10.1002/aic Published on behalf of the AIChE
pressure inside the bubble remains almost ambient. The ultra-
sound wave (which is a longitudinal wave comprising of
alternate compression/rarefaction cycles) also induces high-
velocity oscillatory motion of the fluid elements, commonly
known as microstreaming. However, the liquid properties
such as density and compressibility are not a strong function
of pressure, and, hence, the velocity of microstreaming is not
altered by rise in the static pressure on the liquid medium.
The principal chemical effect of cavitation, popularly
known as the sonochemical effect is generation of highly
reactive radicals such as • H, • O, • OH and HO•2 . These radi-
cals render several beneficial effects on a reaction system
such as induction of stubborn chemical reaction, acceleration
of the reaction kinetics, reduction in the number of steps in
a synthesis or sometimes a switch of reaction pathway. The
principal physical effect of cavitation is generation of strong
convection in the medium due to five phenomena, viz. ultra-
sound oscillatory velocity, microconvection (or microturbu-
lence), microstreaming, shock waves and microjets. As both
physical and chemical effects of cavitation occur on
extremely small spatial and temporal scale, a direct measure-
ment or quantification of these effects would require highly
sophisticated equipment. However, a much easier (and
cheaper) method to get a fairly accurate estimate of the mag-
nitudes of physical and chemical effects of cavitation is
numerical simulations of the bubble dynamics equation,
which we rely on in this study. Modeling of cavitation bub-
ble dynamics is an active area of research for past 3 decades
and various authors have addressed the matter with different
approaches. We refer the reader to our earlier article for a
review of these studies.31 We have used the diffusion limited
ordinary differential equation (ODE) model using boundary
layer approximation proposed by Toegel et al. for our analy-
sis,32 which is based on the comprehensive PDE model of
Storey and Szeri,22 who showed that vapor entrapment in the
cavitation bubble, leading to formation of radicals is essen-
tially a diffusion limited process. Large amount of evapora-
tion occurs at the bubble interface during the expansion
phase of bubble motion, and vapor molecules enter and dif-
fuse toward the bubble core. In the subsequent compression
phase, the same vapor diffuses back and condenses at the
bubble wall. However, in the final moments of bubble com-
pression, velocity of the bubble interface (or bubble wall)
becomes extremely fast and the time scale of bubble motion
becomes smaller than the time scale of vapor diffusion to
bubble wall as well as time scale of condensation (or phase
change) at the bubble wall. As a result, not all of the vapor
that has entered the bubble during expansion can escape dur-
ing compression. The entrapped vapor is subjected to condi-
tions of extreme pressure and temperature reached during
collapse. Dissociation of the vapor molecules occurs at these
conditions resulting in generation of radicals. This model has
been extensively described in our previous articles.33,34 For
the convenience of the reader, we reproduce here only the
main components of the model and relevant data/boundary
conditions. For greater details on this model, we refer the
reader to our earlier articles33,34 as well as the original arti-
cle of Toegel et al.,32 and Storey and Szeri.22
The essential equations and thermodynamic data of this
model have been summarized in Tables 1a and 1b. The main
components of the model are:
1. Keller-Miksis equation for the radial motion of the
bubble.35
2013 Vol. 00 No. 00 AIChE Journal
 Table 1a. Model Equation for Cavitation Bubble Dynamics

Model Component Equation Initial Value

  2    
dR=dt dR2
1. Radial motion 12 dR=dt
c R d R
dt2 þ 3
2 12 3c dt ¼ 1
q 1 þ dR=dt
c ðPi 2Pt Þ þ qRc dPi
dt 24v dR=dt 2r
R 2q R At t 5 0, R 5 Ro, dR/dt 5 0
L L L
of the cavitation
Ntot ðtÞ kT
bubble Internal pressure in the bubble: Pi 5 ½4pðR3 ðtÞ2h3 Þ=3

Pressure in bulk liquid medium: Pt 5 P0 2PA sin ð2pftÞ

 
dNW 2 @CW 2 CW;R 2CW
2. Diffusive flux dt 54pR DW @r jr 5 R  4pR DW ldiff At t 5 0, Nw 5 0
of water qffiffiffiffiffiffiffiffiffiffi 
RDw R
molecules Instantaneous diffusive penetration depth: ldiff 5min jdR=dtj; p
 
dQ 2 @T 2 T0 2T
3. Heat conduction dt 54pR k @r jr5R  4pR k lth At t 5 0, Q 5 0
across bubble qffiffiffiffiffiffiffiffiffiffi 
Rj R
wall Thermal diffusion length: lth 5min jdR=dtj; p

4. Overall energy CV; mix dT=dt5dQ=dt2Pi dV=dt1X ðhW 2UW ÞdNW =dt At t 5 0, T 5 T0
balance Mixture heat capacity: CV; mix 5 CV; i Ni (i 5 N2/O2/H2O)
Molecular properties of water:
Enthalpy: hw 5 4kTo
!
X 3
hi =T
Internal energy: UW 5NW kT 31
i51
exp ðhi =T Þ21
 of various
Heat capacity X  species (i 5 N2/O2/H2O): 
CV;i 5Ni k fi =21 ðhi =T Þ2 exp ðhi =T Þ=ðexp ðhi =T Þ21Þ2

Terms and definitions for Table 1a: R is the radius of the bubble, dR/dt is the bubble wall velocity, c is the velocity of sound in bulk liquid medium, qL is the
density of the liquid, m is the kinematic viscosity of liquid, r is the surface tension of liquid, k is the thermal conductivity of bubble contents, j is the thermal
diffusivity of bubble contents, h is the characteristic vibrational temperature(s) of the species, Nw is the number of water molecules in the bubble, NN2 is the
number of nitrogen molecules in the bubble, NO2 is the number of oxygen molecules in the bubble, t is the time, Dw is the diffusion coefficient of water vapor,
Cw is the concentration of water molecules in the bubble, Cw,R is the concentration of water molecules at the bubble wall or gas-liquid interface, Q is the heat
conducted across bubble wall, T is the temperature of the bubble contents, To is the ambient (or bulk liquid medium) temperature, k is the Bolzmann constant,
hw is the molecular enthalpy of water, Uw is the internal energy of water molecules, fi is the translational and rotational degrees of freedom; CV,i is the heat
capacity at constant volume for species I, Ntot is the total number of molecules (gas 1 vapor) in the bubble, h is the van der Waal’s hard core radius, Po is the
ambient (bulk) pressure in liquid, PA is the pressure amplitude of ultrasound wave, and f is the frequency of ultrasound wave.

Table 1b. Thermodynamic Data for the Model

Degrees of freedom Lennard–Jones force constants Characteristic vibrational

Species (translational 1 rotational) (fi) r (10210 m) e/k (K) temperatures h (K)
N2 5 3.68 92 3350
O2 5 3.43 113 2273
H2O 6 2.65 380 2295, 5255, 5400
Data taken from Hirschfelder et al.41 Condon and Odishaw,42 Reid et al.43

2. Equation for the diffusive flux of water vapor and heat
conduction through bubble wall.
3. Overall energy balance treating the cavitation bubble as
an open system.
The transport parameters for the heat and mass transfer
(thermal conductivity and diffusion coefficient) are deter-
mined using Chapman-Enskog theory using Lennard-Jones
12-6 potential at the bulk temperature of the liquid medium.
Thermal and diffusive penetration depths are estimated using
dimensional analysis. Diffusion of gas across bubble inter-
face is ignored in this model as the time scale for the diffu-
sion of gases is much higher than the time scale for the
radial motion of bubble. The set of four ODEs described in
Table 1a was solved simultaneously using Runge-Kutta
adaptive step-size method.36 We have considered an air bub-
ble (for aerated solutions) and a nitrogen bubble (for deaer-
ated solution using nitrogen sparging) as the cavitation
nuclei for simulations of cavitation bubble dynamics in the
dye solution. The condition for bubble collapse is taken as
the first compression after an initial expansion. Various
parameters used in the simulation of bubble dynamics equa-
tion and their numerical values are as follows: Ultrasound
frequency (f) 5 40 kHz; ultrasound pressure amplitude
(PA) 5 200 kPa; equilibrium bubble radius (Ro) 5 5 lm;
vapor pressure of liquid medium (water) 5 2,500 Pa (calcu-
lated using Antoine type correlation). Various physical prop-
erties of water are as follows: density (qL) 5 1000 kg/m3,
kinematic viscosity (m) 5 1026 Pa-s, surface tension (r) 5
0.072 N/m and velocity of sound (c) 5 1481 m/s. Since the
dyes as well as other components of reaction mixture (H2O2,
FeSO4  7H2O) are present in very small quantities, we have
ignored the change in the physical properties of water with
addition of these chemicals.
Estimation of physical and chemical effects of cavitation
Sonochemical Effect (radical generation by cavitation
bubbles): Using the numerical solution of bubble dynamics
model, one can estimate the composition of the bubble con-
tents at the collapse. Although calculating the composition
of the bubble at the time of collapse, we assume that ther-
modynamic equilibrium is attained.31 The equilibrium mole
fraction of the various species in the bubble at the conditions
of temperature and pressure at first the compression of the

AIChE Journal 2013 Vol. 00 No. 00 Published on behalf of the AIChE DOI 10.1002/aic 5
Figure 2. Experimental results for decolorization of ARB dye solution (10 ppm).
(A) Decolorization under different combinations of ultrasound and Fenton reagents at atmospheric static pressure (A.1 is the time
history of total 60 min reaction, A.2 are the trends of decolorization in the initial 10 min), and (B) effect of static pressure on
decolorization by sono-Fenton process (B.1 is the time history of total 60 min reaction, B.2 are trends of decolorization in the ini-
tial 10 min).

bubble can be calculated using free-energy minimization Results and Discussion

technique.37
Sonophysical Effect of Cavitation: The principal physical
effect of cavitation is generation of convection in the bulk
medium through two phenomena, viz. microconvection,
shock or acoustic waves. These two parameters can be calcu-
lated from numerical result of bubble dynamics model as
follows38–40
2   treatment in the categories involving Fenton reagent. There-
Microconvection: Vturb ðr; tÞ 5 Rr2 dRdt
q d2 Vb
(or acoustic waves): PAW ðr; tÞ5 4pr
Shock
h   Waves i dt2 5
2 d2 R
q Rr 2 dR
dt 1R dt2
where Vb is the volume of the bubble. A representative value
of r is taken as 1 mm. Simulations have been conducted for
the following four conditions (1) air bubble, atmospheric
static pressure, (2) air bubble, elevated static pressure, (3)
nitrogen bubble, atmospheric static pressure, and (4) Nitro-
gen bubble, elevated static pressure.
Experimental results
The time history of decolorization of ARB and BLH dyes
during 60 min of reaction is shown in Figures 2 and 3,
respectively. The decolorization reaction is very fast and it
could be seen from Figures 2 and 3 that for both dyes, most
of the decolorization was achieved in the first 10 min of
fore, in Figures 2 and 3, we have separately depicted the
trends in decolorization of both dyes for the first 10 min in
Figures 2A.2, 2B.2, 3A.2, and 3B.2, with analysis of samples
that were withdrawn every 2 min. The summary of the decol-
orization experiments is given in Table 2, which gives the
extent of decolorization at the end of 10 min as well as
60 min. The time history of decolorization in the first 10 min
was fitted to pseudo first-order kinetics to determine the
kinetic constant of decolorization. We would like to state

6 DOI 10.1002/aic Published on behalf of the AIChE 2013 Vol. 00 No. 00 AIChE Journal
Figure 3. Experimental results for decolorization of BLH dye solution (10 ppm).
(A) Decolorization under different combinations of ultrasound and Fenton reagents at atmospheric static pressure (A.1 is the time
history of total 60 min reaction, A.2 are trends of decolorization in the initial 10 min), and (B) effect of static pressure on decolor-
ization by sono-Fenton process (B.1 is the time history of total 60 min reaction, B.2 are trends of decolorization in the initial
10 min).

that we have not explicitly determined the order of the
decolorization reaction. The decolorization process (which
essentially is the oxidation of the dye molecules induced by
radicals produced during sonication and Fenton reaction)
occurs through series of reactions with several intermediates.
Each of the reaction in decolorization chain will have its
own order and rate constant. In view of this difficulty, and
the limitations of instrumentation used in the study, we have
made a simple approximation of first-order overall reaction
behavior, to get a relative idea of the kinetics of decoloriza-
tion under different experimental conditions. Since most of
the decolorization in experiments employing Fenton reagent
occurred within first 10 min, the first-order kinetic constant
for these experiments was calculated only with the decolor-
ization data for 10 min. The fitness of the pseudo first-order
kinetic model to the experimental data is represented by the
regression coefficient (R2), which is also mentioned in
Table 2. For most cases, the value of R2 was greater than
0.8, which indicates suitability of the pseudo first-order
kinetics for the time data of decolorization.
For categories involving only sonication or sonication
with H2O2, the rate of degradation/decolorization was linear
up to 30 min of treatment, and leveled off thereafter, with
no further decolorization. Some other observations are as
follows:
 Comparing between the two dyes in all categories of
experiments, we see higher decolorization for the BLH
dye, which is a nonazo category dye.
 The total decolorization obtained for both dyes for cate-
gories involving Fenton reagents was significantly
higher than the categories where either sonication alone
or sonication with H2O2 was applied.
 The decolorization kinetics as well as total decoloriza-
tion obtained with Fenton reagent coupled with either
mechanical stirring or ultrasound was similar.

AIChE Journal 2013 Vol. 00 No. 00 Published on behalf of the AIChE DOI 10.1002/aic 7
 Table 2. Summary of Experimental Results

ARB dye (10 ppm) BLH dye (10 ppm)

g (%)a g (%)a
Experimental categories and conditions/composition of k1 k1
reaction mixture in each category 10 min 60 min (min21) 10 min 60 min (min21)
(1) Sonication alone (50 mL dye solution of concn.10 ppm, 0.20 6 0.14 14.04 6 0.04 0.0003 4.24 6 0.38 11.43 6 0.38 0.0047
Po 5 101.3 kPa) (R2 5 0.96) (R2 5 0.98)
(2) Stirring 1 Fenton (50 mL dye solution of concn. 10 76.81 6 1.20 87.72 6 0.68 0.2 95.38 6 0.99 98.68 6 0.38 0.33
ppm 1 2.5 mg FeSO47H2O 1 27 lL 30% H2O2, Po 5 101.3 (R2 5 0.65) (R2 5 0.87)
kPa)
(3) Sonication 1 H2O2 (50 mL dye solution of 10 ppm con- 4.12 6 0.70 13.35 6 0.37 0.004 7.24 6 0.94 38.59 6 0.29 0.0079
cn. 1 27 lL 30% H2O2, Po 5 101.3 kPa) (R2 5 0.91) (R2 5 0.98)
(4) Sonication 1 Fenton (50 mL dye solution of 10 ppm 85.9 6 1.55 91.81 6 0.73 0.25 94.06 6 0.91 100.0 6 0 0.31
concn. 1 2.5 mg FeSO47H2O 1 27 lL 30% H2O2, (R2 5 0.77) (R2 5 0.81)
Po 5 101.3 kPa)
(5) Sonication 1 Fenton (50 mL dye solution of 10 ppm 84.31 6 1.43 92.04 6 0.53 0.24 97.69 6 0.58 100.0 6 0 0.42
concn. 1 2.5 mg FeSO47H2O 1 27 lL 30% H2O2, Po 5 200 (R2 5 0.81) (R2 5 0.96)
kPa)
(6) Sonication 1 Fenton (deaerated solution#, 50 mL dye solu- 69.76 6 1.21 82.72 6 0.93 0.2 92.08 6 1.3 100.0 6 0 0.31
tion of 10 ppm concn. 1 2.5 mg FeSO47H2O 1 27 lL 30% (R2 5 0.51) (R2 5 0.8)
H2O2, Po 5 101.3 kPa)
(7) Sonication 1 Fenton (deaerated solution#, 50 mL dye solu- 81.35 6 1.52 87.04 6 0.53 0.21 89.44 6 1.07 100.0 6 0 0.27
tion of 10 ppm concn. 1 2.5 mg FeSO47H2O 1 27 lL 30% (R2 5 0.85) (R2 5 0.79)
H2O2, Po 5 200 kPa)
a
Initial pH of dye solution in all experiments was 2.0. The decolorization efficiency (g in %, as defined in subsection Experimental procedure), and the kinetic
constant for each experimental category refers to the mean value 6 standard deviation of the three experimental runs in that category.
Deaeration to 2 ppm of dissolved oxygen achieved using sparging the dye solution with nitrogen at flow rate of 40 lit/h, Po is the static pressure on the medium,
k1 is the pseudo first-order kinetic constant calculated on the basis of decolorization obtained in the first 10 min of the reaction, and R2 is the regression
coefficient.

 In case of sonication experiments, addition of H2O2 to
the dye solution alone does not seem to cause any
major change in extent of decolorization of the ARB
dye, although a marginal enhancement in decolorization
of the BLH dye is seen.
 For the sono-Fenton process in aerated dye solution (i.e.,
category 4 and 5 of experiments), the extent of decolor-
ization for both dyes is same for both atmospheric as
well as elevated static pressure. Quite interestingly, in
experimental categories 6 and 7, the extent of decoloriza-
tion by the sono-Fenton process (at both atmospheric and
elevated static pressure) reduces marginally with deaera-
tion (or essentially deoxygenation) of the medium for the
ARB dye. On the other hand, the decolorization of
the BLH dye remains unaffected by the deaeration of the
medium.
Simulations results
As stated earlier, the simulations were carried out for four
conditions for air and nitrogen bubble. Representative simu-
lations results for air bubble at atmospheric static pressure
are shown in Figure 4, while all results have been depicted
in the supplementary material provided with the manuscript.
The summary of the simulations results is given in Table 3a
that lists the peak conditions of temperature and pressure
reached in the bubble at moment transient collapse, the mag-
nitudes of the microconvection velocity and the acoustic
wave generated by the cavitation bubble, and the equilibrium
composition of chemical species generated from dissociation
of gas and water vapor inside the bubble at the moment of
transient collapse. From these results, we can identify some
peculiar features of the cavitation bubble dynamics at the
conditions used in the experiments.
1. Both air and nitrogen bubbles undergo intense collapse
at atmospheric static pressure. The peak conditions
reached in the nitrogen bubble are more intense than
air bubble. The velocity of microconvection generated
by both bubbles is similar, but the acoustic waves emit-
ted by nitrogen bubble are stronger than those by the
air bubble. The extent of water vapor entrapment in
nitrogen bubble is higher than air bubble.
2. Quite interestingly, although the peak conditions of tem-
perature and pressure reached during transient collapse
of air bubbles are lower than nitrogen bubble, the radical
production by air bubble is higher. The number of oxi-
dizing radicals (• O, HO•2 and • OH) produced by the air
bubble at least two fold higher. We attribute this result to
the presence of oxygen in air bubble that conserves the
radicals formed out of dissociation of water vapor.27,28
3. With rise in static pressure to 200 kPa (or 2 bar), both
chemical and physical effects of cavitation bubbles get
eliminated. The radical production in both bubbles
becomes practically nil, and the magnitudes of the
microconvection velocity and pressure amplitude of the
acoustic wave reduces drastically. This essentially means
that the contribution of transient cavitation to the overall
decolorization process is eliminated with rise in static
pressure. Application of high-static pressure in the
medium (greater or equal to the acoustic pressure ampli-
tude) can help in segregation of the effects of ultrasound
and transient cavitation in the medium.
Analysis and discernment of the synergy in sono-Fenton
process
Analysis of the experimental and simulation results con-
currently helps us to discern the mechanism of the hybrid
sono-Fenton process, and also identify the links between
individual (and seeming independent) mechanism of sono-
chemical and Fenton processes. Comparison of results of cat-
egories 1 and 2, where the two techniques were applied
separately, shows that contribution of Fenton process to
overall decolorization is much higher than sonolysis. Com-
parison of decolorization obtained in categories 2 and 4 indi-
cates a very small rise in decolorization with sono-Fenton

8 DOI 10.1002/aic Published on behalf of the AIChE 2013 Vol. 00 No. 00 AIChE Journal

Figure 4. Simulations of radial motion of a 5 lm air
bubble in water.
(f: 40 kHz; PA: 200 kPa; Po: 101.3 kPa (atmospheric).
Time history of (A) radius of the bubble, (B) tempera-
ture inside the bubble, (C) water vapor evaporation in
the bubble, (D) pressure inside the bubble, (E) micro-
turbulence generated by the bubble, and (F) acoustic
waves emitted by the bubble.
process, as compared to Fenton process alone. Practically
same decolorization as in category 4 is obtained in category
5, in which the contribution of transient cavitation effect is
AIChE Journal 2013 Vol. 00 No. 00 Published on behalf of the AIChE
eliminated at elevated static pressure. These results are
clearly indicative of the dominant role played by Fenton pro-
cess over the sonochemical process. The most probable
cause leading to this effect is scavenging of the • OH radicals
generated by the cavitation bubbles by the H2O2 through fol-
lowing reactions,26 which leads to formation of molecular
species causing reduction in the oxidation or decolorization
potential
•
OH 1 H2 O2 ! H2 O 1 HO•2
H• 1 H2 O2 ! HO•2 1 H2
HO•2 1 • OH ! O2 1 H2 O
The synergy in sonochemical and Fenton process thus
seems to be negative.
Another factor leading to smaller contribution of sonolysis
in the sono-Fenton process is the discrete nature of produc-
tion of • OH radicals by cavitation bubbles. The population
or number density of cavitation bubbles in the medium is
not likely to be uniform volumetrically, and so is the produc-
tion of • OH radicals through transient cavitation events. The
concentration of dye molecules in the solution is relatively
small (10 ppm), and, hence, the probability of dye-radical
interaction also comes into picture. Discrete production of
•
OH in the reaction volume, together with low concentration
of dye can lead to lower utilization of the radicals produced
by transient cavitation events for decolorization. The dis-
solved oxygen in the medium is revealed to play major role.
The oxygen can conserve • OH radicals to generate other oxi-
dizing species like • O and • OH2 through reaction26
•
OH 1 O2 ! HO•2 1 O•
At lower concentration of dissolved oxygen (with deaera-
tion of the medium), as in experimental categories 6 and 7,
the conservation action is reduced, which eventually results
in loss of radicals resulting in lower decolorization.
Conclusion
In this study, we have attempted to discern the mechanism
of the hybrid sono-Fenton process for decolorization of the
textile dyes. The concurrent analysis of experimental results
with the simulations of cavitation bubble dynamics reveals
the links and interactions between the individual mechanism
of sonolysis and Fenton process. H2O2 added to the medium
as one of the Fenton reagent scavenges the • OH radicals pro-
duced by cavitation bubbles, which nullify their effect, giv-
ing a negative synergy between sonolysis and Fenton
process. Mere addition of H2O2 to the medium during sonol-
ysis does not give much enhancement to decolorization,
which is attributed to lower vapor pressure of H2O2 due to
which it does not evaporate and dissociate inside the bubble
(to generate additional • OH radicals). Fenton reagent
(Fe21 1 H2O2), on the other hand, gives volumetrically more
uniform production of • OH radicals in the solution, and,
hence, has a dominating contribution to decolorization in the
hybrid process. The role of ultrasound and cavitation in the
hybrid sono-Fenton process is simply physical, i.e., causing
intense mixing in the medium. Radical conservation due to
dissolved oxygen is also revealed to play a major role in
effective utilization of • OH radicals for decolorization.
DOI 10.1002/aic 9
 Table 3a. Summary of the Simulation Results (Air and N2 Bubbles)
Species Parameters for simulations
Air bubble Air bubble Nitrogen bubble Nitrogen bubble
Ro 5 5 lm Ro 5 5 lm Ro 5 5 lm Ro 5 5 lm
Po 5 101.3 kPa Po 5 200 kPa Po 5 101.3 kPa Po 5 200 kPa
Conditions at the first collapse of the bubble
Tmax 5 4013 K Tmax 5 1075 K Tmax 5 4345 K Tmax 5 1106 K
Pmax 5 705.6 MPa Pmax 5 7.78 MPa Pmax 5 786.6 MPa Pmax 5 15 MPa
Vturb 5 0.056 m/s Vturb 5 0.008 m/s Vturb 5 0.054 m/s Vturb 5 0.008 m/s
PAW 5 2.53 MPa PAW 5 0.22 MPa PAW 5 5.89 MPa PAW 5 0.3 MPa
NN2 5 1.306E110 NN2 5 1.306E110 NN2 5 1.653E110 NN2 5 1.653E110
NO2 5 3.471E19 NO2 5 3.471E19 NW 5 2.872E19 NW 5 1.28E19
NW 5 2.026E19 NW 5 9.03E18
Equilibrium composition of species in the bubble at collapse
N2 6.52E–01 7.49E–01 8.26E–01 9.28E–01
O2 1.30E–01 1.99E–01 2.29E–03 0.
H2O 9.21E–02 5.20E–02 1.08E–01 7.20E–02
H 8.15E–04 0. 5.08E–03 0.
O 6.50E–03 0. 1.47E–03 0.
OH 2.56E–02 1.12E–07 1.42E–02 0.
HO2 1.11E–03 0. 8.12E–05 0.
H2O2 1.69E–04 0. 3.65E–05 0.
O3 1.67E–05 0. 5.75E–08 0.
H2 1.79E–03 0. 2.68E–02 6.74E–08
NO 8.79E–02 7.13E–05 1.61E–02 3.11E–08
NO2 1.67E–03 1.98E–05 3.76E–05 0.
HNO 1.55E–04 0. 1.18E–04 0.
HNO2 1.16E–05 0. 8.73E–07 0.
HNO3 1.58E–06 0. 1.48E–08 0.
NH3 1.89E–06 0. 1.24E–04 0.
Terms and definitions for Table 3a: Po is the static pressure in the liquid medium, Ro is initial radius of the cavitation bubble, Vturb is the average velocity of
the microturbulence in the medium generated by ultrasound and cavitation in the medium (estimated at 1 mm distance from bubble center), PAW is the pressure
amplitude of the acoustic wave generated by the cavitation bubble, Tmax is the temperature peak reached in the bubble at the time of first collapse, Pmax is the
pressure peak reached in the bubble at the time of first collapse, NW is the number of water molecules trapped in the bubble, NN2 is the number of N2 molecules
in the bubble, NO2 is the number of oxygen molecules in the bubble, NOH is the number of OH radicals present in the bubble at transient collapse, NH is the
number of H radicals present in the bubble at transient collapse, NO is the number of O radicals present in the bubble at transient collapse, NHO2 is the number
of HO2 radicals present in the bubble at transient collapse, and NH2O2 is the number of H2O2 molecules present in the bubble at transient collapse.

Table 3b. Net Production of Various Oxidizing Species per Bubble

Air bubble Air bubble N2 bubble N2 bubble
Parameter (Po 5 101.3 kPa) (Po 5 200 kPa) (Po 5 101.3 kPa) (Po 5 200 kPa)
NOH 4.75E18 1.95E13 2.75E18 0.
NO 1.2E18 0. 2.85E17 0.
NHO2 2.06E17 0. 1.58E16 0.
NH2O2 3.14E16 0. 7.08E15 0.

Acknowledgments 7. Gogate PR, Pandit AB. A review of imperative technologies for

The authors are grateful to the anonymous referees of this
article for their meticulous assessment of this manuscript
and constructive criticism.
Literature Cited
1. Peralta-Zamora P, Kunz A, de Moraes SG, Pelegrini R, de Campos
Moleiro P, Reyes J, Duran N. Degradation of reactive dyes I. A
comparative study of ozonation, enzymatic and photochemical proc-
esses. Chemosphere. 1998;38:835–852.
2. Lin JJ, Zhao XS, Liu D, Yu ZG, Zhang Y, Xu H. The decoloration
and mineralization of azo dye C.I. Acid Red 14 by sonochemical
process: Rate improvement via Fenton’s reactions. J Hazard Mater.
2008;157:541–546.
3. Wu CH. Decolorization of C.I. reactive red 2 in O3, Fenton-like and
O3/Fenton-like hybrid systems. Dyes Pigm. 2008;77:24–30.

4. Papić S, Vujevć D, Koprivanac N, Sinko D. Decolorization and min-
eralization of commercial reactive dyes by using homogeneous and
heterogeneous Fenton and UV/Fenton process. J Hazard Mater.
2009;164:1137–1145.
5. Patidar R, Khanna S, Moholkar VS. Physical features of ultrasound
assisted enzymatic degradation of recalcitrant organic pollutants.
Ultrason Sonochem. 2012;19:104–118.
6. Gogate PR, Pandit AB. A review of imperative technologies for
wastewater treatment I: oxidation technologies at ambient conditions.
Adv Environ Res. 2004;8:501–551.
wastewater treatment II: hybrid methods. Adv Environ Res. 2004;8:
553–597.
8. Segura Y, Molina R, Martinez F, Melero JA. Integrated heterogene-
ous sono-photo Fenton processes for the degradation of phenolic
aqueous solutions. Ultrason Sonochem. 2008;16:417–424.
9. Segura Y, Martinez F, Melero JA, Molina R, Chand R, Bremner
DH. Enhancement of the advanced Fenton process (Fe0/H2O2) by
ultrasound for the mineralization of phenol. Appl Catal B Environ.
2012;113-114:100–106.
10. Huang R, Fang Z, Yan X, Cheng W. Heterogeneous sono-
Fenton catalytic degradation of bisphenol A by Fe3O4 magnetic
nanoparticles under neutral condition. Chem Eng J. 2012;197:
242–249.
11. Babuponnusami A, Muthukumar K. Advanced oxidation of
phenol: A comparison between Fenton, electro-Fenton, sono-electro-
Fenton and photo-electro-Fenton processes. Chem Eng J. 2012;183:
1–9.

12. Grčić I, Sipić A, Koprivanac N, Domagoj V. Global parameter of
ultrasound exploitation (GPUE) in the reactors for wastewater treat-
ment by sono-Fenton oxidation. Ultrason Sonochem. 2012;19:
270–279.
13. Oezdemir C, Oeden MK, Sahinkaya S, Kalipci E. Color removal
from synthetic textile wastewater by sono-Fenton process. Clean:
Soil Air Water. 2011;39:60–67.
14. Ozdemir C, Oden MK, Sahinkaya S, Guclu D. The sonochemical
decolorization of textile azo dye CI reactive orange 127. Color Tech-
nol. 2011;127:268–273.

10 DOI 10.1002/aic Published on behalf of the AIChE 2013 Vol. 00 No. 00 AIChE Journal
15. Zhong X, Royer S, Zhang H, Huang Q, Xiang L, Valange S, Barrault
J. Mesoporous silica iron-doped as stable and efficient heterogeneous
catalyst for the degradation of C.I. Acid Orange 7 using sono-photo-
Fenton process. Sep Purif Technol. 2011;80:163–171.
16. Sundararaman TR, Ramamurthi V, Partha N. Decolorization and
COD removal of Reactive yellow 16 by Fenton oxidation and com-
parison of dye removal with photo Fenton and sono Fenton process.
Mod Appl Sci. 2009;3:15–22.
17. Bremner DH, Molina R, Martınez F, Melero JA, Segura Y. Degrada-
tion of phenolic aqueous solutions by high frequency sono-Fenton sys-
tems (US-Fe2O3/SBA-15-H2O2). Appl Catal B Environ. 2009;90:
380–388.
18. Molina R, Martınez F, Melero JA, Bremner DH, Chakinala AG.
Mineralization of phenol by a heterogeneous ultrasound/Fe-SBA-15/
H2O2 process: Multivariate study by factorial design of experiments.
Appl Catal B Environ. 2006;66:198–207.
19. Bianchi CL, Pirola C, Ragaini V, Selli E. Mechanism and efficiency
of atrazine degradation under combined oxidation processes. Appl
Catal B Environ. 2006;64:131–138.
20. Andreozzi R, Caprio V, Insola A, Marotta R. Advanced oxidation
processes (AOP) for water purification and recovery. Catal Today
1999;53:51–59.
21. Shah YT, Pandit AB, Moholkar VS. Cavitation Reaction Engineer-
ing. New York: Plenum Press/Kluwer Academic; 1999.
22. Storey BD, Szeri AJ. Water vapor, sonoluminescence and sonochem-
istry. Proc R Soc Lond Ser A. 2000;456:1685–1709.
23. Hart EJ, Henglein A. Sonochemistry of aqueous solutions: hydrogen-
oxygen combustion in cavitation bubbles. J Phys Chem. 1987;91:
3654–3656.
24. Suslick KS. Sonochemistry. Science 1990;247:1439–1445.
25. Sivasankar T, Paunikar AW, Moholkar VS. Mechanistic approach to
enhancement of the yield of a sonochemical reaction. AIChE J.
2007;53:1132–1143.
26. Frenklach M, Bowman T, Smith G, Gardiner B. Reaction rate coeffi-
cients. Gri-MechTM Website: http://www.me.berkeley.edu/gri-mech/
data/frames.html). Accessed January 2013.
27. Sivasankar T, Moholkar VS. Mechanistic approach to intensification
of sonochemical degradation of phenol. Chem Eng J. 2009;49:57–69.
AIChE Journal 2013 Vol. 00 No. 00 Published on behalf of the AIChE
28. Sivasankar T, Moholkar VS. Physical insights into the sonochemical
degradation of recalcitrant organic pollutants with cavitation bubble
dynamics. Ultrason Sonochem. 2009;16:769–781.
29. Chakma S, Moholkar VS. Mechanistic features of ultrasonic desorp-
tion of aromatic pollutants. Chem Eng J. 2011;175:356–367.
30. Moholkar VS, Warmoeskerken MMCG, Ohl, CD, Prosperetti A.
Mechanism of mass-transfer enhancement in textiles by ultrasound.
AIChE J. 2004;50:58–64.
31. Krishnan JS, Dwivedi P, Moholkar VS. Numerical investigation into
the chemistry induced by hydrodynamic cavitation. Ind Eng Chem
Res. 2006;45:1493–1504.
32. Toegel R, Gompf B, Pecha R, Lohse D. Does water vapor prevent
upscaling sonoluminescence? Phys Rev Lett. 2000;85:3165–3168.
33. Sivasankar T, Moholkar VS. Mechanistic features of the sonochemical
degradation of organic pollutants. AIChE J. 2008;54:2206–2219.
34. Kumar KS, Moholkar VS. Conceptual design of a novel hydrody-
namic cavitation reactor. Chem Eng Sci. 2007;62:2698–2711.
35. Keller JB, Miksis MJ. Bubble oscillations of large amplitude.
J Acoust Soc Am. 1980;68:628–633.
36. Press WH, Teukolsky SA, Flannery BP, Vetterling WT. Numerical
Recipes. New York: Cambridge University Press; 1992.
37. Chemical equilibrium calculation. Bioanalytical Microfluidics
Program, Colorado State University Website. http://navier.engr.colo
state.edu/dandy/code/code-4/index.html. Accessed January 2013.
38. Leighton TG. The Acoustic Bubble. San Diego: Academic Press;
1994.
39. Grossmann S, Hilgenfeldt S, Zomack M, Lohse D. Sound radiation of
3 MHz driven gas bubbles. J Acoust Soc Am. 1997;102:1223–1227.
40. Moholkar VS, Warmoeskerken MMCG. Integrated approach to opti-
mization of an ultrasonic processor. AIChE J. 2003;49:2918–2932.
41. Hirschfelder JO, Curtiss CF, Bird RB. Molecular theory of gases and
liquids. New York: Wiley, 1954.
42. Condon EU, Odishaw H. Handbook of Physics. New York: McGraw
Hill; 1958.
43. Reid RC, Prausnitz JM, Poling BE. Properties of Gases and Liquids.
New York: McGraw Hill; 1987.
Manuscript received Jan. 28, 2013, and revision received Apr. 16, 2013.
DOI 10.1002/aic 11